US2837574A - Chlorination of alcohols - Google Patents
Chlorination of alcohols Download PDFInfo
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- US2837574A US2837574A US571598A US57159856A US2837574A US 2837574 A US2837574 A US 2837574A US 571598 A US571598 A US 571598A US 57159856 A US57159856 A US 57159856A US 2837574 A US2837574 A US 2837574A
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- 238000005660 chlorination reaction Methods 0.000 title description 7
- 150000001298 alcohols Chemical class 0.000 title description 6
- 150000001875 compounds Chemical class 0.000 claims description 21
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 5
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- AGYUOJIYYGGHKV-UHFFFAOYSA-N 1,2-bis(2-chloroethoxy)ethane Chemical compound ClCCOCCOCCCl AGYUOJIYYGGHKV-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- JYYNAJVZFGKDEQ-UHFFFAOYSA-N 2,4-Dimethylpyridine Chemical compound CC1=CC=NC(C)=C1 JYYNAJVZFGKDEQ-UHFFFAOYSA-N 0.000 description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2,5-dimethylpyridine Chemical compound CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- JBIJLHTVPXGSAM-UHFFFAOYSA-N 2-naphthylamine Chemical compound C1=CC=CC2=CC(N)=CC=C21 JBIJLHTVPXGSAM-UHFFFAOYSA-N 0.000 description 1
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical class CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000520223 Helice Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- -1 triethylene glycol Ammonium chloride Chemical compound 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/12—Saturated ethers containing halogen
Definitions
- Our invention relates to an improved method for the chlorination of alcohols in order to replace the hydroxyl groups present therein with chlorine.
- Our invention is particularly concerned with the chlorination of alcohols of the formula: R'O(RO),,ROH, wherein R is hydrogen or an alkyl radical containing from 1 to 4 carbon atoms, R is an alkylene radical containing from 2 to 3 carbon atoms and n is an integer from 0 to 5, in order to produce the corresponding compounds wherein the hydroxyl groups are replaced by chlorine atoms.
- the alcohols described above are treated with sulfur monoor di-chloride in the presence of catalytic amounts of compounds containing a basic nitrogen atom.
- compounds for example, pyridine; lower alkylated pyridines, such as, alpha picoline, beta picoline, gamma picoline, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine; and the monoethyl pyridines; quinoline; isoquinoline; aniline and lower N-alkyl anilines such as dimethyl aniline and diethyl aniline; alpha naphthylamine; beta naphthylamine; ethylene diamine; triethylene tetramine; and so forth.
- the addition salts of such compounds with strong inorganic acids such as the hydrohalides and the hydrogen sulfates are also suitable.
- Ammonium chloride also acts as a catalyst, but we consider the use of other compounds such as pyridine to be preferable.
- Sulfur monochloride has been previously used to accomplish the above-mentioned chlorination. This is disclosed in Organic Preparations by Weygand (Interscience, 1945) on page 99, where trimethylene glycol is shown to be converted to 1-chloro-3-hydroxypropane in 60 percent yield. The replacement of the second hydroxyl group is more difficult, however, and we have found that such dichloro compounds are obtainable only in 3040 percent yield in the absence of a catalyst. As a result of our attempts to improve the yields of the reaction between sulfur chlorides and the alcohols,-we have discovered that yields of over 70 percent of dichloro products can be realized if the reaction is completed in the presence of at least one of the abovementioned compounds.
- the method employed in carrying out our invention involves premixing sulfur monoor di-chloride with the alcohol, adding the catalyst, heating the mixture at a temperature of 100 C. to 200 C. for one to five hours, and separating the product by any suitable atent O means.
- the alcohol employed as a starting material is a monohydric alcohol
- the molar ratio of the sulfur chloride, i. e. sulfur monochloride or sulfur dichloride, to alcohol employed be within the range from 1:1 to 1221.
- the alcohol employed as a starting material is a dihydric alcohol
- the molar ratio of the sulfur chloride, i. e. sulfur monochloride or sulfur dichloride to alcohol employed be within the range from 2:1 to 24:1.
- the reactants can be premixed in any order, we have found it preferable to slowly add the sulfur chloride to the alcohol while maintaining the temperature of the mixture below about 60 C. by external cooling.
- the catalyst Upon completion of the mixing the catalyst is added, preferably to the extent of from 0.1 to 1 percentby weight of the total reactants, although up to 2 percent at times advantageous. The use of more than about 2 percent substantially does not increase the yield, and becomes uneconomical.
- the catalysts can be added either as free bases, or as the addition salts of strong inorganic or mineral acids. Although it is thought that the salt is the actual catalyst, there is noparticular advantage in using it, since the hydrogen chloride byproduct quickly forms such a salt with the free base if the latter is used.
- the product can be efiiciently recovered by vacuum distillation followed by fractionation. by treating the product with active carbon.
- Example I The reactor consisted of a 3-necked flask equipped during the addition. The addition required 64 minutes to complete during which time the temperature was maintained at 44 to 55 C. At the end of this time 22 grams of pyridine, or about 1 percent by weight, was added to the reaction mixture. The ice bath was then removed, and the temperature was raised to between and C. and maintained there for one hour. The product was separated from the reaction mixture by takeover distillation at a pressure of. 4-7 mm. of Hg and then'isolated by fractionation through a 30 inch glass helice packed column. It boiled at 124 C./ 17 mm. Hg. The 883 grams of product so recovered was treated with 1 percent of Nuchar C--N (proprietary active carbon) for one hour at 100 C. In this way there was recovered852 grams or 76 percent of the theory of purified 1,2 bis(beta-chloroethoxy) ethane,
- Example 11 Again using the apparatus as described in Example I, 209 grams of sulfur dichloride was added to 240 grams Further purification can be accomplishedv 3 of Z-methoxy-Z'-hydroxydiethyl ether. quired 55 minutes during which time the temperature was maintained at 13-23 C. The ice bath in which the reaction flask had been immersed was then removed.
- Example III 570 grams of sulfur monochloride was placed in an apparatus described .in Example I. To this there was added 300 grams of triethylene glycol over a period of minutes, the temperature increasing from 28 C. to 64 C. At the end of this time, 8.7 grams of aniline hydrochloride was placed in the reaction flask and its temperature was raised to 180 C. and maintained there for one hour and minutes. was recovered 247 grams of 1,2-bis(beta-chloroethoxy) ethane, or 65 percent of the theory.
- Example IV The procedure of Example III was followed for four other catalysts. The catalyst and the yield obtained therewith are listed below:
- the reactionmix Upon distillation, there The addition re- 4 ether of dipropylene glycol, the monoethyl ether of dipropylene glycol, the mono-n-butyl ether of dipropylene glycol and the like.
- a method for the replacement of the hydroxyl radicals of compounds of the formula RO(RO),,ROH with chlorine which comprises reacting a compound of the formula RO(RO),,ROH with a compound selected from the group consisting of sulfur mono-chloride and sulfur dichloride while the reactants are in admixture with a catalytic amount of a material containing a basic nitrogen atom, R being selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, R being an alkylene radical containing from 2 to 3 carbon atoms and n being an integer from 0 to 5 2.
- the method of claim 1 wherein said compound is triethylene glycol.
- a method for the replacement of the hydroxyl radicals of compounds of the formula HO(RO),,ROH with chlorine which comprises reacting a compound of the formula HO(RO),,ROH with a compound selected from the group consisting of sulfur mono-chloride and sulfur dichloride while the reactants are in admixture with a catalytic amount of a material containing a basic nitrogen atom, R being an allzylene radical containing from 2 to 3 carbon atoms and n being an integer from O to 5.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States CHLORINATION F ALCOHOLS No Drawing. Application March 15, 1956 Serial No. 571,598
12 Claims. (Cl. 260-615) Our invention relates to an improved method for the chlorination of alcohols in order to replace the hydroxyl groups present therein with chlorine. Our invention is particularly concerned with the chlorination of alcohols of the formula: R'O(RO),,ROH, wherein R is hydrogen or an alkyl radical containing from 1 to 4 carbon atoms, R is an alkylene radical containing from 2 to 3 carbon atoms and n is an integer from 0 to 5, in order to produce the corresponding compounds wherein the hydroxyl groups are replaced by chlorine atoms.
Prior to our invention such chlorinations have been accomplished in various less advantageous ways, the most recent being the use of the expensive thionyl chloride as the chlorinating agent.
It is an object of our invention to provide a novel, practical, and economical method for the production of the above described chlorides in good yields. Another object is to effect the chlorination with the readily available surfur chlorides. Still a further object is to increase the yields over those of the prior art by the use of suitable catalysts. These and other objects will be apparent from the following description.
According to our invention the alcohols described above are treated with sulfur monoor di-chloride in the presence of catalytic amounts of compounds containing a basic nitrogen atom. Among such compounds are, for example, pyridine; lower alkylated pyridines, such as, alpha picoline, beta picoline, gamma picoline, 2,3-lutidine, 2,4-lutidine, 2,5-lutidine; and the monoethyl pyridines; quinoline; isoquinoline; aniline and lower N-alkyl anilines such as dimethyl aniline and diethyl aniline; alpha naphthylamine; beta naphthylamine; ethylene diamine; triethylene tetramine; and so forth. The addition salts of such compounds with strong inorganic acids such as the hydrohalides and the hydrogen sulfates are also suitable. Ammonium chloride also acts as a catalyst, but we consider the use of other compounds such as pyridine to be preferable.
Sulfur monochloride has been previously used to accomplish the above-mentioned chlorination. This is disclosed in Organic Preparations by Weygand (Interscience, 1945) on page 99, where trimethylene glycol is shown to be converted to 1-chloro-3-hydroxypropane in 60 percent yield. The replacement of the second hydroxyl group is more difficult, however, and we have found that such dichloro compounds are obtainable only in 3040 percent yield in the absence of a catalyst. As a result of our attempts to improve the yields of the reaction between sulfur chlorides and the alcohols,-we have discovered that yields of over 70 percent of dichloro products can be realized if the reaction is completed in the presence of at least one of the abovementioned compounds.
In general, the method employed in carrying out our invention involves premixing sulfur monoor di-chloride with the alcohol, adding the catalyst, heating the mixture at a temperature of 100 C. to 200 C. for one to five hours, and separating the product by any suitable atent O means. Where the alcohol employed as a starting material is a monohydric alcohol, we prefer that the molar ratio of the sulfur chloride, i. e. sulfur monochloride or sulfur dichloride, to alcohol employed be within the range from 1:1 to 1221. Where the alcohol employed as a starting material is a dihydric alcohol, we prefer that the molar ratio of the sulfur chloride, i. e. sulfur monochloride or sulfur dichloride, to alcohol employed be within the range from 2:1 to 24:1. Although the reactants can be premixed in any order, we have found it preferable to slowly add the sulfur chloride to the alcohol while maintaining the temperature of the mixture below about 60 C. by external cooling.
I Upon completion of the mixing the catalyst is added, preferably to the extent of from 0.1 to 1 percentby weight of the total reactants, although up to 2 percent at times advantageous. The use of more than about 2 percent substantially does not increase the yield, and becomes uneconomical. The catalysts can be added either as free bases, or as the addition salts of strong inorganic or mineral acids. Although it is thought that the salt is the actual catalyst, there is noparticular advantage in using it, since the hydrogen chloride byproduct quickly forms such a salt with the free base if the latter is used.
When the reaction is complete the product can be efiiciently recovered by vacuum distillation followed by fractionation. by treating the product with active carbon.
The following examples clearly illustrate a method of putting this invention into practice while placing no limitations thereon.
Example I The reactor consisted of a 3-necked flask equipped during the addition. The addition required 64 minutes to complete during which time the temperature was maintained at 44 to 55 C. At the end of this time 22 grams of pyridine, or about 1 percent by weight, was added to the reaction mixture. The ice bath was then removed, and the temperature was raised to between and C. and maintained there for one hour. The product was separated from the reaction mixture by takeover distillation at a pressure of. 4-7 mm. of Hg and then'isolated by fractionation through a 30 inch glass helice packed column. It boiled at 124 C./ 17 mm. Hg. The 883 grams of product so recovered was treated with 1 percent of Nuchar C--N (proprietary active carbon) for one hour at 100 C. In this way there was recovered852 grams or 76 percent of the theory of purified 1,2 bis(beta-chloroethoxy) ethane,
Example 11 Again using the apparatus as described in Example I, 209 grams of sulfur dichloride was added to 240 grams Further purification can be accomplishedv 3 of Z-methoxy-Z'-hydroxydiethyl ether. quired 55 minutes during which time the temperature was maintained at 13-23 C. The ice bath in which the reaction flask had been immersed was then removed.
About 4.5 grams or 1 percent by weight of pyridine was added to the reaction flask and the temperature thereof was raised to and maintained at 140 C. for 1 hour and 20 minutes. ture was distilled to recover Z-methoXy-Z-chlorodiethyl ether. The latter was then subjected to fractional distil lation through a 30 inch, glass-helice packed. column with triethylene glycol dimethyl ether as chaser. In this way 188 grams of 2-methoxy.-2'-chlorodiethyl ether, or 68 percent of the theoretical yield, was recovered, boiling point 165-167 C./747 mm., 1.4285.
Example III 570 grams of sulfur monochloride was placed in an apparatus described .in Example I. To this there was added 300 grams of triethylene glycol over a period of minutes, the temperature increasing from 28 C. to 64 C. At the end of this time, 8.7 grams of aniline hydrochloride was placed in the reaction flask and its temperature was raised to 180 C. and maintained there for one hour and minutes. was recovered 247 grams of 1,2-bis(beta-chloroethoxy) ethane, or 65 percent of the theory.
Example IV The procedure of Example III was followed for four other catalysts. The catalyst and the yield obtained therewith are listed below:
Wt. percent catalyst based Catalyst on weight of Yield,
sulfur dichloride Percent and triethylene glycol Ammonium chloride l 54 Dimethyl aniline-.- 1 52 Ureae. 1 49 Diethylenetriamine 3HCL 2 46 glycol, the monomethyl ether of monoethylene glycol,
the monoethylether of monoethylene glycol, the monon-butyl ether of monoethylene glycol, the monomethyl ether of diethylene glycol, the monobutyl ether of diethylene glycol, the monoethyl ether of triethylene glycol, the monomethyl ether of monopropylene glycol, the monoethyl ether of monopropylene glycol, the monon-butyl ether of monoethylene glycol, the monomethyl At the end of this time the reactionmix Upon distillation, there The addition re- 4 ether of dipropylene glycol, the monoethyl ether of dipropylene glycol, the mono-n-butyl ether of dipropylene glycol and the like.
We claim:
1. A method for the replacement of the hydroxyl radicals of compounds of the formula RO(RO),,ROH with chlorine which comprises reacting a compound of the formula RO(RO),,ROH with a compound selected from the group consisting of sulfur mono-chloride and sulfur dichloride while the reactants are in admixture with a catalytic amount of a material containing a basic nitrogen atom, R being selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, R being an alkylene radical containing from 2 to 3 carbon atoms and n being an integer from 0 to 5 2. The method of claim 1 wherein said compound is triethylene glycol.
3. The method of claim 1 wherein said compound is Z-methoxy-T-hydroxy diethyl ether.
4. The method of claim 1 wherein said sulfur chloride is sulfur monochloride.
5. The method of claim 1 wherein said sulfur chloride is sulfur dichloride.
6. The methodof claim 1 wherein said material is pyridine. v
.7. The method of claim 1 wherein said material is aniline hydrochloride.
8. The method of claim 1 wherein said compound is triethylene glycol, wherein said sulfur chloride is sulfur dichloride and wherein said material is pyridine.
9. The method of claim 1 wherein said compound is 2-methoxy-2'-hydroxy diethyl ether, wherein said sulfur chloride is sulfur dichloride and wherein said material is pyridine.
10. The method of claim 1 wherein said compound is triethylene glycol, wherein said sulfur chloride is sulfur monochloride and wherein said material is aniline hydrochloride.
'11. The method of claim 1 wherein said compound is tetraethylene glycol.
12. A method for the replacement of the hydroxyl radicals of compounds of the formula HO(RO),,ROH with chlorine which comprises reacting a compound of the formula HO(RO),,ROH with a compound selected from the group consisting of sulfur mono-chloride and sulfur dichloride while the reactants are in admixture with a catalytic amount of a material containing a basic nitrogen atom, R being an allzylene radical containing from 2 to 3 carbon atoms and n being an integer from O to 5.
References Cited in the file of this patent Derick et al.: I. Am. Chem. Soc., vol. 38 (1916), page 2481.
Ephraim: Inorganic Chemistry, 4th ed. (1947), pages 595, 601.
Ahmad et 21.: J. Am. Chem. Soc., vol. (1948), pages 3391, 3392.
Wagner et 21.: Synthetic Organic Chem. (1953), page 92.
Claims (1)
1. A METHOD FOR THE REPLACEMENT OF THE HYDROXYL RADICALS OF COMPOUNDS OF THE FORMULA R''O(RO)NROH WITH CHLORINE WHICH COMPRISES REACTING A COMPOUND OF THE FORMULA R''O(RO)NROH WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF SULFUR MONO-CHLORIDE AND SULFUR DICHLORIDE WHILE THE REACTANTS ARE IN ADMIXTURE WITH A CATALYTIC AMOUNT OF A MATERIAL CONTAINING A BASIC NITROGEN ATOM, R'' BEING SELECTED FROM THE GROUP CONSISTING OF HYDROGEN ALKYL RADICALS CONTAINING FROM 1 TO 4 CARBON ATOMS, R BEING AN ALKYLENE RADICAL CONTAINING FROM 2 TO 3 CARBON ATOMS AND N BEING AN INTEGER FROM 0 TO 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US571598A US2837574A (en) | 1956-03-15 | 1956-03-15 | Chlorination of alcohols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US571598A US2837574A (en) | 1956-03-15 | 1956-03-15 | Chlorination of alcohols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2837574A true US2837574A (en) | 1958-06-03 |
Family
ID=24284339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US571598A Expired - Lifetime US2837574A (en) | 1956-03-15 | 1956-03-15 | Chlorination of alcohols |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2837574A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3294847A (en) * | 1962-09-11 | 1966-12-27 | Rohm & Haas | Method for the preparation of ethercontaining chlorides |
| US3325548A (en) * | 1963-03-28 | 1967-06-13 | Rohm & Haas | Method for the preparation of alkoxyethoxyethyl chlorides |
| US5002678A (en) * | 1990-06-29 | 1991-03-26 | Olin Corporation | Lubricants for heat transfer fluids |
| US20120088745A1 (en) * | 2003-12-16 | 2012-04-12 | Fishburn C Simone | Chemically modified small molecules |
| US20140275657A1 (en) * | 2013-03-14 | 2014-09-18 | Shin-Etsu Chemical Co., Ltd. | Method for producing chlorohydrocarbon having conjugated double bonds |
-
1956
- 1956-03-15 US US571598A patent/US2837574A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3294847A (en) * | 1962-09-11 | 1966-12-27 | Rohm & Haas | Method for the preparation of ethercontaining chlorides |
| US3325548A (en) * | 1963-03-28 | 1967-06-13 | Rohm & Haas | Method for the preparation of alkoxyethoxyethyl chlorides |
| US5002678A (en) * | 1990-06-29 | 1991-03-26 | Olin Corporation | Lubricants for heat transfer fluids |
| US20120088745A1 (en) * | 2003-12-16 | 2012-04-12 | Fishburn C Simone | Chemically modified small molecules |
| US20210393513A1 (en) * | 2003-12-16 | 2021-12-23 | Nektar Therapeutics | Chemically modified small molecules |
| US12016952B2 (en) * | 2003-12-16 | 2024-06-25 | Nektar Therapeutics | Methods of preparing a monodisperse oligo(ethylene glycol) reagent composition |
| US20140275657A1 (en) * | 2013-03-14 | 2014-09-18 | Shin-Etsu Chemical Co., Ltd. | Method for producing chlorohydrocarbon having conjugated double bonds |
| US9845273B2 (en) * | 2013-03-14 | 2017-12-19 | Shin-Etsu Chemical Co., Ltd. | Method for producing chlorohydrocarbon having conjugated double bonds |
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